Method for making flexible, vapor-permeable, water-resistant vinyl films and the like having improved slip and hand



Jan- 14, 1958 R. E. scHoRNsTHElMER ET AL 2,819,981

METHOD FOR MAKING FLEXIBLE, VAPOR-PERMEABLE, WATER-RESISTANT VINYL FILMS AND THE LIKE HAVING IMPROVED SLIP AND HAND Filed Feb. 25, 1955 1 1121110@ Q 11.211.101, 1z mm w1. 5,1m. 15.2119 1 oz11 o mE P 115;., 11.. 115s 11h 1t 1w mmm |l. 1 WMC u lnonPnwM 11:... 19.1 n H H o1 11 o1 1. 11 woms &w .L m EH T 11.010 1.5.6 v. 1011.1 zo 1111 7.9110 o ..11 .BM V--. lil. L 1 .291.10 R 15.6 115 1o ....1210 zo 1111 o 11 w. ..o1 ,.1,.1. 11.6 1o 15.6 zo n. E P 11 @2.55 oo 1 .w11n. 15.6 zo .20.10 ...Vom.1.1o1 00 m WmID L N5m2 m 1121119,J Qz

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United tates Patent`4 rmrrron ron Martirio FLEXIBLE, .VAPOR-naa; Manara, wArnnnnsrsrANr vietri. arm/rs xtsnrna man nar/ING tMPnovEnsLrr AND HAND Robert E. Sehornstheiiner and Hpgl1 P. Campbell',

Marietta, Ohio, assignors .to The'B.- F. Goodrich Company, New York, N. Y., a. corporationof-New .York

Application February 23, 31955, Serial l"lt`).-490,142y

12 Claims (Cl. 111-11) This invention relates to a method` of making plastic films, sheets andthe like. More specifically, it relates to a method for obtaining a flexible, vapor-permeab1e,-rwater resistant thermoplastic coated fabric having` excellent hand and slip Plastics such as polyvinyl chloride andA the.like.have excellent wearing properties, lend themselves-well to vari ous colors and to embossingto create novel designs, and can easily be cleaned. However, when they arefused as coatings vor lms on fabric bases to make upholstery ma\ terial `for furniture, automobilesand the`like,.ithasbeen. found that` the lms which are nonporous trap water, ormoisture condenses on their surface,-` so that theytend tolstick to the individual who comes in contactrwiththem or'cause the individuals clothes' to` adhere to. his skin.

Accordingly, such materials are uncomfortable.- If.` holes it is known that very useful vinyl lms and vinyl coated' fabrics can beobtained by incorporating into the vinyl mixture a powdered or finely-divided nonhygr'oscopic pore-forming materialrsoluble in a nonsolvent for the polymeric composition. After fusing, the polymer can then be washed to remove the nonhygroscopicmaterial to provide a water-resistant vapor permeable vinyl polymer lm orv coated fabric. These breathable lms or coated fabrics are also washable and dirt resistant and do not. tend to stick to the individual who comes in contact with it nor to cause clothes to stick to the individual.'

In processing such vinyl compounds with the powdered or nely-divided f nonhygroscopic pore-forming materialr on. a rubbenor plastic calender, the operation -is difficult unless more plasticizer is used than is desired to ob# tain a finished vinyl .product'with the required hand :and sli`p`, characteristics after the pore former'is washed out. The coating after washing is somewhat softand clothing does notslipfreely across its surface. Hand is :a term usedA in the upholstery industry yand refers 'to 'the v relative softness,- stiffness, flexibility, etc., of` a materialV asl it feels to'the'hand. Slipisf anotherterm usedlin` the upholstery industry and refers to the ease'or diculty with' which clothing slips over the surfaceof a material.

In other words, for manyapplications especially yinthe upholstery industry i it is preferred '-to have material with Vime theproper-fhand and slip but due to the fact that it is diicult to process the vinyl containing the pore-forming element, excess plasticizer is used making the finally fused vinyl coating too'softtgive the best hand and s1ip. If the amount of krthe lplasticizer is redcedto improvethe slip and hand,thepolymericcomposition becomes diicult to mix, calender, laminate oi' spread coat so that processing costs'lar'e `in'cr'easedf- Moreover; if thesurfac offthe polymeric llm 'or coating-is givent a-toptcoat'f-ofthe sama or-A` other polymer tol improve its' appearance; andfeel; additional costs are i involved in `-the extra.fprocessirigl steps and 'material' thaty are required Hence, it is 'a primaryobject of th'e'- present inventionV to` avoid thef diculties alluded-'to'hereinbefore*aiidlt providela method for producing awater-resistanti vaporpermeable' polymeric lfilm with` improved hand andl sl'ipL It? isf another object-of 'thisinventio'n to-provide-afmetllf od L for producing afi thermoplastic polymeric resin-coated fabric base which is flexible, water-resistant, vaporper# meabl'e andwherein saidfcoating-exhibits excellent hand andlslipl and: is 'adliere'ntl tothefbasez Thse. and= other'objects' andi advan'tages'- of the p'rsent inventionzwllk become more' apparent maniere"v skilled inntlie art" fro'mltheffollowing'detailedfdescription andi example'. p

Accordingy to :'th'e'fpre'sentt .inventionA it: has, been?` diss covered fthat afvapor.' permeable, wate'rresis-tant fexbl coating-."ontilm'.offafplasticized polymeric'materi-al' hav# ing excellent handlfandf slipcan'nowheobtained by? incorporating a'lminor amount'. of asoft'energsluhlein a nonsolvent for'fthe polym'ericimateria'lg:` asaireplaeeme'nt for part ofor inaddition to the?plasti'cizernfacomposi#S tion comprising.Lthepolymeric1 materialgl the plastic-iz'er andfa pore-formingmaterial prior to lca'lendering 'on'fcastl ings. The;v composition/'can 'thenfibe -"`cas`ti` or"y calendered'," fused, embossed if desired, and treated withfa solventftoy remove the softener andtpore'forming material',l Clothing slipsv 'readily across `the surface of 'the yresulting ico'a'tingfor' lmt Air-canlea'sily passthroughf thedlr'n'i I-lovtfever, water'doesnotreadily, if' at all, penetrate the fflm'i Which actually-can withstand a hydrostatic-head of-upftoiSS/f" orfmore of water. The films or' layersare ver-y abrasione.: resistant' and their surfacesfare relatively hard;Y1 Theyf also 'canbe fdeposited as plasticized` compositionrcoati'ngslf onlsupport-ing bases'or websto Iformadherent"flexiblen water-resistant, vapor-permeable' laminates .havingrsliclc and shiny polymeric coatings.l

Thesoftener used in the present compositionssolublei inta solvent which isf a nonsolvent-for'the polymeric'm'aff terial'and its plasticizer. ltv also is compatible inthe 'pla's-f ticized polymericpore-forming.y `composition y'so'I that= AtheV compositionV can readily be mixed,calendered, lamina-tech#` for-med Tinto plastisols; embossed and .thelike' yet'can'rea'd-i-i ly-be-,rem'oved by the'solventwithout detractingwfromfthei: propertiesfof'the 'plasticizedv polymer: A'featur'eot the# use of theiisoftening Sagent is thatfsince itiisfremovedilayv asolvent itcan replace part offthefpore-frining natei'allwith'retention of the desired'vapor-permeabilityand sistanee to' penetration byfwater, Examples of suitable' softeners for use in the compositions"disclosed` 'hrein^ areth alkylene carbonates and the polyalkyleneglycols'.- Specic examples'of suchA compounds'are eth`ylen`e"car.V bonate, propylene carbonate, butylene carbona'tf, PQly ethylene glycol, polypropyleneglycol and 'the like. f Mix-' tures of :the softenerscan be used.` The alkylenecarbone. atesl can be made by` reacting 2* mols4 of an-alkylenet alcohol or its sodium derivative with a material such as phosgene. For example,

Hz H2C=CHO =0 aNaCl /0 H2o=orrom Polyalkylene glycols have the general formula HO CH2 (CHZOCHZ X.CH2OH wh'ere x is an integer. They have various molecular weights. For example, one member of the series can be prepared by condensing 2 mols of the monosodium salt of diethylene glycol with 1 mol of B,B'dichloroethyl ether to give hexaethylene glycol dichloride which is condensed with 2 mols of the monopotassium salt of hexaethylene glycol yielding an 18 membered compound. Polyalkylene glycols of even higher polymer numbers can be made and are known to the art. Other methods for making the carbonates and glycols discussed above can be employed. Moreover, other softeners exhibiting the aforementioned properties can be used in the polymeric materials disclosed herein.

Very minor amounts of the softener, as compared to the plasticizer, afford some improvement in the processability of the composition and in the appearance and feel of the resulting breathable film. However, for best results it is preferred to use a total amount of from about 5 to 30% by weight of the softener based on the total weight of the softener and plasticizer in the composition. Very large amounts of the softener are not desired for after washing or extraction of the softener from the lm, the flexibility and elasticity of the film are too low.

The softener can be added to a plastisol, organosol or plastigel composition of the polymer prior to or after adding the pore-forming material. Likewise when using a Banbury or a roll mill the softener can be added to the polymer prior to, at the same time, or after the plasticizer, pore-forming material and other compounding ingredients have been added.

The polymeric material used in practice of the present invention includes all of the haloethylene polymers composed predominantly of a polymerized haloethylene having from one to two halogen atoms attached to only one of the carbon atoms, such as homopolyrners of vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene uoride and the like, and interpolymers or copolymers of two or more of these monomers. Copolymers or interpolymers made from monomeric mixtures containing at least one haloethylene monomer together with a lesser amount of one or more copolymerizable monoolefnic monomers can also be employed. Monoolefinic materials which can be coor interpolymerized with the haloethylene monomers include vinyl esters such as vinyl acetate, vinyl chloroacetate, vinylv propionate, vinyl chloropropionate, vinyl butyrate, vinyl benzoate, vinyl chlorobenzoate, and others; acrylic and alpha-alkyl acrylic acids, their alkyl esters, their amides and their nitriles such as acrylic acid, chloroacrylic acid, methacrylic acid, ethacrylic acid, methyl arylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, 2ethylhexyl acrylate, n-decyl acrylate, methyl methacrylate, butyl methacrylate, methyl ethacrylate, ethyl ethacrylate, acrylamide, N-methyl acrylamide, N,Ndimethyl acrylamide, methacrylamide, N-methyl methacrylamide, N,Ndimethyl methacrylamide, acrylonitrile, chloroacrylonitrile, methacrylonitrile, ethacrylonitrile, and the like; vinyl aromatic compounds such as styrene, dichlorostyrene, vinyl naphthalene and others; alkyl esters of fumarie and maleic acids such as dimethyl maleate, diethyl maleate, and others; vinyl alkyl ethers and ketones such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, 2-chloro-ethyl vinyl ether,

methyl vinyl ketone, ethyl vinyl ketone, isobutyl vinyl ketone, etc.; and in addition other monooleiinic materials such as ethyl methylene malonate, ethylene, isobutylene, trichloroethylene, vinyl pyridine, N-vinyl carbazole, N- vinyl pyrrolidone, and various other readily polymerizablc compounds containing a single olenic double bond, especially those containing the CH2=C group. When utilizing interpolymers or copolymers, the proportions of the various monomers in the monomeric mixtures polymerized to give the interpolymer may be varied considerably as long as the haloethylene monomer constitutes at least 50% by weight of the total. For example, there may be used copolymers of from 50 to 99%, preferably from 70 to 95%, by weight of the haloethylene monomer, together with from l to 50%, preferably from 5 to 30%, by weight of a vinyl ester, or an acrylic or methacrylic ester or any of the other monoolefinic materials mentioned above, or any two, three, four, or more of these. Tripolymers of from 50 to 90% by weight of vinyl chloride, from 5 to 45% by Weight of vinylidene chloride, and from 5 to 45% by weight of a vinyl ester such as Vinyl acetate or vinyl benzoate, or an acrylic or methacrylic ester are examples of vinyl halide polymers which may be used. Of the various polymers disclosed herein, those composed of a vinyl halide, especially vinyl chloride, and of a predominant amount of a vinyl halide and of a minor amount of a vinylidene halide, especially copolymers of a predominant amount of vinyl chloride and a minor amount of vinylidene chloride, and blends of these polymers and copolymers are preferred. Blends or mixtures of the homopolymers, copolymers and interpolymers can also be used. Where the haloethylene polymer is to be calendered onto the fabric base, the polymer prior to mixing with plasticizer may be in the form of pellets, granules or powder. However, when making plastisols and the like used for spread coating, the polymer should be in the form of powder and may be porous.

Examples of suitable plasticizers for the haloethylene polymers are butyl benzyl phthalate, dicapryl phthalate,V

dioctyl adipate, dioctyl azelate, dioctyl sebacate, dioctyl phthalate, dibutyl phthalate, dibutoxy ethyl phthalate, dibutyl sebacate, octyl diphenyl phosphate, tricresyl phosphate, tributoxyethyl phosphate, or mixtures thereof. Other plasticizers which can be employed are hexachlorodiphenyl oxide, toluene sulfonamide-aldehyde resin, and a composition comprising a water-insoluble thermoplastic cellulose ether, di(4tertiary butyl phenyl) monophenyl phosphate and di(4tertiary butyl phenyl) mono(5tertiary butyl-2xenyl) phosphate. Still other plastlctzers for haloethylene containing polymers Well known to the art can be used.

The total amount of plasticizer and softener used in the composition will vary from about 30 to 200 parts by weight per parts by weight of the polymeric material. The resulting unfused compositions containing also the pore-forming material will be in the form of dry pourable powders or pourable liquid masses. On fusing, flexible, relatively hard (as compared to compositions having a higher plasticizer content), films or coatings with desired slip and hand characteristics will be obtained. It however, is preferred to employ a total of from about 50 to 100 parts by weight of plasticizer and softener for each 100 parts of the polymeric material present, especially where a calender mix is to be laminated onto a fabric base and later embossed to which the present invention is particularly directed. When making a calender mix the softener, plasticizer and polymeric material may be mixed in a Banbury or other suitable mixer and the tempera ture may go above the gel point and as high as about 340 F. while, when making plastisols, the temperature during mixing should be below the gel point and preferably not above room temperature, about 25 C., to provide a liquid composition having a viscosity of from 200 to 40,000 centipoises and up to 130,000 centipoises.

fPlastigels vrare `prepared by adding a minor-amount of a thickening agent such as a metallic soap (aluminum distearate, calcium stearate, `lithium distearate, lithium hydroxy stearate, magnesium stearate, sodium stearate or mixtures thereof) to the plastisol compositions described above. Generally, 5 to l0 parts by weight of said soap Vare used for every 100 parts by weight of plastisol. The plastigels are putty-like masses and retain their form when embossed and after embossing can be fused at a ytemperature of from about 300 to 400 F. It will be understood that a minor amount of the soap used in forming plastigels may come out of the plastic when it is Washed with a solvent such as water to remove the softener and pore-forming material. However, a major amount of the soap remains in the plastic so that water may AIbe considered a nonsolvent in such cases for the thickening agent.

Organosols are obtained by adding a minor amount, Vl0 .to 50% by weight based on the weight of the plastisol, of a volatile organic diluent such as mineral spirits, toluene, and the like and mixtures thereof to the above described plastisol composition or by replacing -part of the plasticizer with diluent. Organosols are more fluid than plastisols and are desirable to use where increased iiuidity is needed or where some penetration of the fabric base `is indicated.

The pore-forming material should be nonhygroscopic yand insoluble or only sparing soluble in the polymer, .plasticizer and other compounding ingredients but should be soluble in a nonsolvent for the polymer, plasticizer .and other compounding ingredients. Moreover, it should be a solid and not melt, soften, decompose or react in 'the `'polymeric composition at fusing or embossing temperatures. Materials found useful .as pore-forme'rs are the alkaline halide salts such as ammonium chloride, sodium lchloride, potassium chloride, sodium bromide, potassium bromide, and the like and mixtures thereof which 'are readily soluble in water which is essentially va nonsolvent for 'the polymeric composition. Other mate- 'rials exhibiting the aforementioned properties can likewiserbe used in the practice of the present invention. The :nonhygroscopic material may be added to the polymer- `plasticizer-softener mix inthe Eanbury or to the mix on the mill rolls if mill mixing is used. lt also can be mixed -with the plastisol, plastigel or organosol during formation ofthese compositions or after they have been formed taking care to avoid yraising the temperature much above room temperature, as in the case of the plastisols, to avoid gelling.

The nonhygroscopic, pore-forming material should be in a finely-divided or powdered condition to provide after removal from the polymer very small pores or a microporous structure in which substantially all, or all of the pores are interconnecting. Preferably essentially all of the particles should pass through about a 65 mesh USS screen and a predominant amount through about a 100 mesh USS screen. While particles of a somewhat larger size can be employed, they should not be in chunk form or of a granulated size since the structure formed is too porous and wiil not retain a static head of Water. Moreover, a film or sheet having large pores does not present a continuous, smooth and uninterrupted surface as is exhibited by the product of the present invention where the pores in the film are just barely Visible Vto the naked eye when looking at the cut edge of the film. Furthermore, large pores tend to collect and retain dust, dirt, and the like. On the other hand, somewhat smaller `mesh size salt can be used4 but it should not be very substantially finer than that shown 'above to avoid loss of vapor permeability. The amount of pore-forming material will vary from about 50 to 300% by weight based on the weight of the polymer in the composition. Larger or smaller amounts of the pore yformer rare undesirable as t 6 such tend to decrease Avapor permeability .orflower water resistance. v

The polymeric haloethylene compositions disclosed herein may also contain minor amounts of one or more stabilizers such as the alkaline earth silicates, basic ilead carbonate, barium ricinoleate, lead oxide, Alead silicate, lead stearate, lead phenolate, titanium dioxide, and the like. Desirably such stabilizers are used in an amount of from 0.11 to l0 partslby weight per 100 parts by weight of the haloethylene polymer.

Other compounding ingredients kmay also be incorporated in the fhaloethylene polymer or polymer composition such as fillers, dyes and color pigments, herbicides, fermicides, fungicides, minor amounts of rubber.;I butadiene-1,3 and acrylonitrile copolymers, and the like. Detergents such as Sotex CW (compounds of long-chain fatty acid esters of multiple ether amine Ylinkages),Sa'nto merse S (salts of substituted aromatic -sulfonic acids), Aerosol 18 (N-octadecyl disodium sul-fosuccinamate), and the like, in amounts of from 0.5 to 5 parts by weight per parts of polymer may be added `to the composition.

The porous web or fabric base which is desirably used to support the polymer is preferably constructed `of the open-weave type which is capable of elongation, such as netting, although other weaves such as drill, twill and the like may be used. Weftless fabric kas well as unwove'n materials, i. e., matted materials, may also be used. While sized fabric can be used, it is preferred to employ unsized fabric. The fabric itself may be of cotton, Wool, or other natural fibrous materials, paper, synthetic fibers, or mixtures thereof, which are capable of withstanding the fusing temperatures of haloethylene polymers without appreciably losing their shape, strength `and Ithe like.

If desired, the fabric can lfirst be treated with an adhesive (about l ounce per `square, yard) and dried'to provide increased adhesion between the polymer and the fabric base although satisfactory adherence `has been `obtained without using adhesives. Where plastisols 'and organosols are employed, an adhesive-coated base fabric is desired to reduce penetration of plasticized polymer into and between the interstices of the cloth and to `reduce stiffening of the finally obtained laminate. Examples of suitable adhesives are plasticized polyvinyl chloride latices, latices of mixtures of copolymers of butadiene- 1,3 and acrylonitrile and polyvinyl chloride, and the like.

The solvent used to remove the softener can be any solvent which will dissolve, extract orremove the softener without dissolving or essentially dissolving out the polymeric material, its plasticizer and other necessary cornpounding ingredients. The solvent used may also be the same as the solvent employed for removal `of the poreforming material so that dissolving out, extracting or washing out the softener and pore-forming material can be accomplished in one step. Water has been found to be an admirable substance for use vas a solvent since it removes the softener and pore former at thejsame time. However', other solvents can be used to remove both the softener and pore former, or each one separately, before or after the other. Mixtures of solvents ycan be employed.

The solvent used to remove the softener vand A'poreforming material also can contain from about 0.01 to .50% by weight of a detergent or other vmaterial yto increase the wettability of the solvent for the softener and pore-forming material contained in the polymer composition. The time vof washing `may vary from a few minutes to several hours or more depending on the amount of softener and pore-forming material, thickness of coating, degree of agitation, method of washing, etc. After washing, the `sheet or .laminate may -be dried in air at room temperature -or heated `in -an oven ata temperature of from about 10G-175 F. or higher. nThe wash water remaining after washing can betheated to evaporate the water, or it can be flashed, and vthe 4,pore

former and softener recovered for further use. They can be separated by heating to a temperature suflicient to 'melt the softener which then can be removed easily from the pore former especially' where it is a material such as salt or NaCl.

Several methods may be used to prepare water-resistant, vapor-permeable plastic polymeric haloethylene coated fabrics as shown in the accompanying drawing which is a flow sheet illustrating the sequence of successive steps which may be followed in practicing the present invention. For example, the polymeric material in dry powder or granular form is mixed with sufficient plasticizer to plasticize the polymer, softener and pore former in a'Banbury or other mixer at about 340 F., warmed on rolls, applied to cloth, preferably heated, by calendering and laminating at about 250-500 F. and washed to remove the softener and pore formed. If it is desired to provide a design on the surface of the polymer, the hot polymer-coated fabric may be passed through embossing rolls prior to washing. If the polymer has cooled, it can be reheated and embossed. It is much preferred to emboss prior to washing to avoid closing the pores of the polymer under the design of the embossing roll. Instead of using a dry powdered or granular polymer, the Banbury may be charged with a plastisol. Plastigels or organosols may also be charged to the Banbury but they offer little advantage as they are more economically spread onto the fabric. Moreover, both sides of the fabric may bc coated and additional polymer coatings may be applied to the polymer coating on the fabric base if deemed necessary by using any one of the procedures disclosed herein.

Other methods of applying the polymeric composition to the fabric base may also be used. For example, the composition is calendered and the fabric is run between the last two rolls of the calender machine with the composition banked onto the fabric. Or, the composition is calendered and the fabric is run over a rubber laminating roll which laminates the fabric to the sheet on the last roll of the calender. Still another process is to calender a sheet of the composition and feed the composition sheet to a separate laminator where the composition sheet and fabric are laminated together between the two pressure rolls of the laminator.

In spread coating the fabric base, a plastisol is generally used although plastigels or organosois may also be employed. The plastisol mix is cast, roller coated or spread on the fabric base, heated to gel and fuse and washed to remove the softener and pore former. Embossing of the polymer-coated fabric, if desired, should precede washing. 1f a thinner composition is desired, an organosol can be used and sufficient time should be allowed during the heating step to permit evaporation of the diluent from the organosol. Additional equipment to carry off the vapors of the diluent or to prevent explosions or lires may be required when using the organosol composition.

Moreover, plastisols or organosols can be cast or spread as a film or sheet onto a belt of stainless steel or other material to which it will not adhere readily. A fabric web is then laminated to the cast film before or after fusing. After fusing the film, the laminate is readily stripped from the belt and washed. Alternatively, the plastisol or organosol can be cast onto such a belt, fused, cooled, stripped off the belt and laminated or cemented to the fabric base and washed. Or, the fused film can be washed and then cemented to the base.

The plastigel mix is prepared and handled in much the same way as the plastisol composition. It is spread onto the fabric base and embossed or a design pressed on its surface, fused, and washed to remove the softener and pore former. Alternatively, the embossing or pressing step can be omitted although the use of embossing a prior to fusing is a feature of the use of plastigels which "retain their form when embossed. Moreover, emboss- 8 ing may follow the fusing or washing steps but such procedure is not too desirable.

While the foregoing comments have largely been directed to vapor-permeable water-resistant haloethylene polymer coatings or films laminated to a supporting fabric base, it will be understood that useful slick and shiny vapor-permeable and water-resistant films, sheets and the like of haloethylene polymers of the proper hardness for good hand and slip characteristics can be obtained which are unsupported. They can be prepared by calendering, casting or spread coating the polymer mix on a belt such as stainless steel. After setting or fusing the polymer, it can be stripped from the base material such as a stainless steel belt and washed or cooled and washed.

The slick and shiny fused polymeric films and coatings obtained according to the present invention are about .010 to .030" thick. Thinner or thicker films and coatings can of course be obtained by varying the spacing between the calender rolls or the amount of plastisol, etc., used. However, very thin coatings are not desirable as they may result in loss of strength while very thick coatings are not too desirable as they tend to reduce moisture vapor transmission. The films, coatings and laminated fabrics of the present invention are flexible, water-resistant and vapor-permeable. The Water vapor transmission of the fused polymer will vary from about 50 to 200 grams H2O/100 in.2/24 hrs. and the hydrostatic pressure (Suter) will vary from about 15 to 35 in. H2O. The abrasion resistance index (using double rubs with sandpaper) of the film will be from 2,000 to 8,000. The fused polymeric films and laminates are easy to wash and do not hold dirt or other foreign matter and can be embossed, preferably prior to removal of the softener and pore former, to stimulate leather, special fabric weaves, etc. In addition to embossing, the material can be printed with decorative or leather-like designs, etc., and can be top-coated by printing, spraying, spreading or roller coating to improve slip, hand, and abrasion resistance without appreciably detracting from its vapor permeability either before or after washing out the softener and pore former. Such procedures also do not adversely affect the ease of washing out the softener and pore former. However, an important feature of the present invention is the obtainment of results equal to or better than those achieved with top coating so that this step is unnecessary and undesirable.

The following example will serve to illustrate the invention with more particularity to those skilled in the art:

Plasticized compositions were prepared by mixing the ingredients listed below in a laboratory pony mixer, banburying and milling to consistency:

Antimony oxide.

Rose color paste Polypropylene glycol (Dow P750 Propylene carbonate The USS screen size of the salt was as follows:

1% retained on #65 mesh 1% retained on #80 mesh 14% retained on #100 mesh 84% through #100 mesh .af-eregast The stabilizer and lubricant paste v:comprised "about:

2.07% dioctyl phthalate 36.08% Harshaw Chem. Co. Z-V-l stabilizer (cadmium organic octyl hexyl phenyl phosphite complex) 24.05% Harshaw Chem. Co. 7V-l .stabilizer (epoxy and chelating composition) 36.08% barium stearate 1.72% calcium silicate Table MVT, Composition on fabric gms. Appearance of` Feel of coating used H2O/l0() coating km2/24 hours 130 Nonspecular Leathery. 140 Sh' Hard and slick.

Do. Do.

The Suter hydrostatic pressure of the above laminates varied from about 18 to l27 in. H2O. The foregoing results -show that the use of a softener, soluble in a nonsolvent for the plasticizer and polymer, will provide improvements in slip and hand lofthe resulting coating without a loss in its useful vapor 'permeability or `water resistance. Moreover,while composition"B also exhibited a shiny, hard and :slick surface, it required about 30 minutes more milling `time `and .a higher ternperature and pressure when it vwas sheeted ,out into a film. Calendering composition B was more diflicult than calendering the other composition.

In summary, the present invention 'teaches that thin, water-resistant, vapor-permeable films, sheets and laminates exhibiting excellent hand and slip canreadily be prepared from compositions of polymers or copoly- .mers of haloethylene compounds, a plasticizer, 4a minor amount of a softener for said polymer, soluble in a non- `solvent for the polymer and plasticizer, and a linelydivided nonhygroscopic pore-forming material also soluble in a nonsolvent `for said polymer and plasticizer, and removing said softener and pore former vfrom the fused or set plasticized polymerbytreatment with 'a`so1- vent which is a nonsolvent for the polymer and plasticizer. Thenovel products of the method of thepresent invention are smooth and can be embossed tto simulate leather and materials of various kinds as well vvas lcertain novel weaves and other designs. They twill find vutility as upholstering materialin furniture such vvas chairs, automobile seats, clothing, footwear and the like and especially Where a breathable, Water-resistant plastic coating or tilm having a hard, shiny or glossy and slick finish is desired.

What is claimed is:

l. The method which comprises mixing together to form a nonaqueous polymeric composition a polymer of a monomeric material in which each monomeric constituent contains a single olelinic double bond and in which the predominant monomer is a haloethylene having from l to 2 halogen atoms on only one carbon atom, a plasticizer for said polymer, a water-soluble softener for said polymer and from about 50 to 300% by weight based on the weight of the polymer of a solid, finely-divided, nonhygroscopic water-soluble pore-forming material, forming a relatively thin continuous fused layer of fsaid :composition and treating said `:layer with an v'aqueous :solution to vremove .said softener Aand said nonhygroscopic material to provide "a slick and shiny, vapor-permeable, water-resistant layer of .said polymeric Vcomposition with improved hand and slip characteristics, said softener and said plasticizer being present yin a total .amount of yfrom about 30 to 200 parts by weightper parts by weight of said polymer and said softener being present in a minor amount as compared to fsaid plasticizer.

2. ln the method of making a breathable, water-resistant plasticmaterial by mixing together a polymerof a monomeric material in which leach monomeric `constituent contains a single oleiinic double bond andin which the predominant monomer is a haloethylene having from l to 2 halo-gen atoms on only one carbon atom, a plasticizer for said polymer, and .from about 50 to 300% by weight based on the weight of said polymer of a finely,- divided, solid, nonhygroscopic water-soluble, pore-forming material to formi a nonaqueous composition, forming a continuous layer offsaid composition, fusing the .resulting layer and treating thesame with an aqueous solution to remove said nonhygroscopic material, the improvement comprising adding a water-soluble softener during said mixing step to at least one of said components of said composition and prior to fusing said composition, said softener and said plasticizer being present in a total amount of from about 30 to 200 parts by weight per 100 parts by Weight of said polymer and said softener being present in a minor amount as compared to said plasticizer.

3. The method `which comprises mixing together .to form a nonaqueous polymeric composition a polymer of a `monomeric material in which each imonomeric constituent contains .a single oleinic double bond and in which the predominant monomer is .a haloethylene .having from l to 2 halogen-atoms on only one carbon atom, a softener selected from the class consisting of watersoluble alkylene carbonates yand polyalkylene glycols, a plasticizer for said polymer and .from about 50% to .300% by weight based .on the weight of said polymeric .rn-aterial .of a solid, powdered, nonhygroscopic water-.soluble pore-forming material, forming a continuous, thin, liexible and adherent fused layer of said plastic composition :on at least one vside of a porous fabric base, and treating `said fused layer with an aqueous solution toremove said softener and said powdered nonhygroscopic material from said plastic composition to provide a slick and shiny,

vapor-permeable, water-.resistanttiexible'polymeric coated .laminate fwith improved :slip and :hand characteristics,

ysaid softener andi-said plasticizerbeing 'present in'atotal amount of .from about 50 to 100 parts `by '.weightperlGO parts by @weightfof said `polymer and said :softener fbeing present in an amount of from about 5 to 30% by 'weight ofthe total amount of said'softener and said plasticizer.

4. The method which comprises'mixing together below gelling temperature to form a homogenous appearing nonaqueous composition a polymer of a monomeric mafterial 'in which each monomeric constituent contains a 'single .oleiinic double bond and tin which the .predominant kmonomer is a .haloethylene having from l to v2 halogen atoms on only one carbon atom, a plasticizer for said polymer to form a plastisol, a watensoluble softener for said polymer and from about 50 to 300% by weight based on the weight of said polymer of a solid, powdered, non-hygroscopic water-soluble pore-forming material, essentially all of the particles of said non-hygroscopic material passing through about a 65 mesh USS screen and a predominant amount of said particles passing through about l0() mesh USS screen, spreading the resulting composition as a continuous, relatively thin coating on at least one side of a porous fabric base, heating said coating to fuse the same, and washing the resulting laminate containing said fused coating with an aqueous solution to remove said softener and said nonhygroscopic material from said coating to obtain a laminate containing a Water-resistant, vapor-permeable plasticized polymeric coating exhibiting improved hand and slip characteristics, said softener and said plasticizer being present in a total amount of from about 50 to 100 parts by Weight per 100 parts by weight of said polymer and said softener being present in an amount of from about to 30% by weight of the total amount of said softener and said plasticizer.

5. The method which comprises mixing together to form a homogenous appearing nonaqueous composition a polymer of a monomeric material in` which cach monomeric constituent contains a single olefinic double bond and in which the predominant monomer is a haloethylene having from 1 to 2 halogen atoms on only one carbon atom, a plasticizer for said polymer, a minor amount of a thickening agent to form a plastigel, a water-soluble softener for said polymer and from about 50 to 300% by Weight based on the Weight of said polymer of a powdered, nonhygroscopic, solid water-soluble pore-forming material, essentially ail of the particles of said non-hygroscopic material passing through about a 65 mesh USS screen and a predominant amount of said particles passing through about a 100 mesh USS screen, spreading the resulting plastigel composition as a continuous, relatively thin coating on at 'least one side of a fabric base, heating said coating to fuse the same, and washing said base containing said fused coating with an aqueous solution to remove said softener and said nonhygroscopic material from said coating to provide a water-resistant, vapor-permeable plasticized polymeric coating exhibiting improved hand and slip characteristics, said softener and said plasticizer being present in a total amount of from about 50 to 100 parts by weight per 100 parts by weight of said polymer and said softener being .present in an amount of from about 5 to 30% by weight of the total amount of said softener and said plasticizer.

6. The method which comprises mixing together to form a homogenous appearing nonaqueous composition a polymer of a monomeric material inwhich each monomeric constituent contains a single olenic double bond and in which the predominant monomer is a haloethylene having from 1 to 2 halogen atoms on only one carbon atoms, a plasticizer for said polymer, from l0 to 50% by weight based on the Weight of the polymer and plasticizer of a volatile organic diluent to form an organosol, a water-soluble softener for said polymer and from about 50 to 300% by weight based on the weight of the polymer of a solid, timely-divided, nonhygroscopic water-soluble pore-forming material, essentially all of the particles of said n-onhygroscopic material passing through about a 65 mesh USS screen and a predominant amount of said particles passing through about a 100 mesh USS screen, forming a continuous, thin layer of the resulting composition on a porous fabric base, evaporating said diluent, fusing said layer, and Washing said layer with an aqueous solution to remove said softener and said nonhygroscopic material from said composition to provide a vapor-permeable, water-resistant plasticized polymeric layer exhibiting improved hand and slip characteristics, said softener and said plasticizer being present in a total amount of from about 50 to 100 parts by weight per 100 parts by Weight of said polymer and said softener being present in an amount of from about 5 to 30% by weight of the total amount of said softener and said plasticizer.

7. The method which comprises mixing together to form a homogenous appearing nonaqueous composition a polymer of a monomeric material in which each monomeric constituent contains a single olefinic double bond and in which the predominant monomer is a haloethylene having from 1 to 2 halogen atoms on only one carbon atom, a plasticizer to plasticize said polymeric material, a water-soluble softener for said polymer and from about 50 to 300% by weight based on the weight of said polymer of a powdered, nonhygroscopic, solid, water-soluble,

pore-forming material, essentially all of the particles of said nonhygroscopic material passing through about a mesh USS screen and a predominant amount of said particles passing through about a mesh USS screen, calendering the resulting composition as a continuous, rela.` tively thin coating on at least one side of a porous fabric base, fusing said coating, and treating said coating with an aqueous solution to remove said softener and said nonhygroscopic material from said coating to provide a Waterresistant, vapor-permeable plasticized polymeric coating r exhibiting improved hand and slip characteristics, said softener and said plasticizer being present in a total amount of from about 50 to 100 parts by weight per 100 parts by weight of said polymer and said softener being present in an amount of from about 5 to 30% by weight of the totai amount of said softener and said plasticizer.

8. The method according to claim 7 in which said softener is ethylene carbonate.

9. The method according to claim 7 in which said softener is propylene carbonate.

10. The method according to claim 7 in which said softener is butylene carbonate.

11. The method according to claim 7 in which said softener is polyethylene glycol.

12. The method according to claim 7 in which said softener is polypropylene glycol.

References Cited in the le of this patent UNITED STATES PATENTS 1,953,083 Lawson Apr. 3, 1934 2,277,747 Dreyfus Mar. 3 l, 1942 2,474,201 Raymond et al June 21, 1949 2,517,646 Ewing Aug. S, 1950 2,542,527 Honey et al Feb. 20, 1951 2,601,255 Bruson June 24, 1952 2,603,575 Schramm July 15, 1952 2,635,093 Miller et al Apr. 14, 1953 2,673,825 Biefeld Mar. 30, 1954 2,697,664 Goeser et al Dec. 2l, 1954 2,698,816 Dosrnann et al Jan. 4, 1955 2,711,996 Hofrichter June 28, 1955 2,719,795 Nottebohm Oct. 4, 1955 2,721,150 Grantham Oct. 18, 1955 2,721,151 Grantham Oct. 18, 1955 

1. THE METHOD WHICH COMPRISES MIXING TOGETHER TO FORM A NONAQUEOUS POLYMERIC COMPOSITION A POLYMER OF A MONOMERIC MATERIAL IN WHICH EACH MONOMERIC CONSTITUENT CONTAINS A SINGLE OLEFINIC DOUBLE BOND AND IN WHICH THE PREDOMINANT MONOMER IS A HALOETHYLENE HAVING FROM 1 TO 2 HALOGEN ATOMS ON ONLY ONE CARBON ATOM, A PLASTICIZER FOR SAID POLYMER, A WATER-SOLUBLE SOFTENER FOR SAID POLYMER AND FROM ABOUT 50 TO 300% BY WEIGHT BASED ON THE WEIGHT OF THE POLYMER OF A SOLID, FINELY-DIVIDED, NONHYGROSCOPIC WATER-SOLUBLE PORE-FORMING MATERIAL, FORMING A RELATIVELY THIN CONTINUOUS FUSED LAYER OF SAID COMPOSITION AND TREATING SAID LAYER WITH AN AQUEOUS SOLUTION TO REMOVE SAID SOFTENER AND SAID NONHYGROSCOPIC MATERIAL TO PROVIDE A SLICK AND SHINY, VAPOR-PERMEABLE, WATER-RESISTANT LAYER OF SAID POLYMERIC COMPOSITION WITH IMPROVED HAND AND SLIP CHARACTERISTICS, SAID SOFTENER AND SAID PLASTICIZER BEING PRESENT IN A TOTAL AMOUNT OF FROM ABOUT 30 TO 200 PARTS BY WEIGHT PER 100 PARTS BY WEIGHT OF SAID POLYMER AND SAID SOFTENER BEING PRESENT IN A MINOR AMOUNT AS COMPARED TO SAID PLASTICIZER. 